Ceramic high dielectric composition

ABSTRACT

In a ceramic dielectric composition with BaTiO 3  as host material, CaTiO 3  and Sb 2  O 3  are added to be contained, and besides thereto any one of Nd 2  O 3 , La 2  O 3  and Sm 2  O 3  are added to be included, thereby ceramic dielectric composition having high dielectric constant, small voltage dependency of characteristics, large bending force, and small equivalent series resistance in high frequency range is provided. 
     Also, by having BaTiO 3  as host material and adding CaTiO 3  and Ta 2  O 5  thereto, and further adding Sb 2  O 3  or Pr 6  O 11 , similar superior characteristics to the above-mentioned ceramic high dielectric composition is obtainable. 
     Besides, by adding SiO 2  to the above-mentioned ceramic high dielectric compositions, strength is further increased. 
     These ceramic dielectric composition of high dielectric constant is suitable for, for example, dielectric substance of laminated ceramic capacitor.

DESCRIPTION

1. Technical Field

The present invention relates to ceramic high dielectric composition to be used mainly as laminated ceramic capacitor.

2. Background Art

Hitherto many proposals have been made on ceramic high dielectric compositions with barium titanate (BaTiO₃) as host material, and they have been used specially for disc type ceramic capacitors.

The barium titanate is a material having ferrodielectric characteristic, and its Curie point lies around 120° C. Demarcated by this 120° C., in the lower temperature side thereof it becomes tetragonal, and in the upper temperature side thereof it becomes cubic. And it is well known that in the tetragonal region it shows ferrodielectric characteristic and in the cubic region it shows paraelectric characteristic.

Since, ceramic of such sole barium titanate has a very large change of dielectric constant dependent on temperature and also has a large dielectric dissipation (tan δ) in a temperature range of about normal temperature, it is hardly used as capacitor independently; and hitherto devices are made to shift the Curie point to around the normal temperature and to decrease the temperature dependency by adding various additives. CaTiO₃, BaZrO₃, SrTiO₃, BaSnO₃ and etc. are known as representative of the additives. By adding these appropriately and by adjusting with a small amount composition, material having characteristics of X7R, Y5T, Y5V, Z4V and etc. of EIA (Electronic Industries Association) standard are offered. The fact is that these materials have been hitherto utilized generally as ceramic capacitors of thick disc type, for instance having 0.5-1 mm thickness of element.

In these years, miniaturization of capacitors is progressing corresponding to miniaturization of various electronics-related components, and the most in laminated ceramic capacitors. The laminated layer ceramic capacitor is that in which ceramic dielectric body is made into thin film of around 25-100 μm and sandwiching comb type electrodes to form a multiple layer structure. And since a ratio of electrodes area to electrodes gap can be made very large, its capacitance per volume can be made as large as 100 times or larger in comparison with the ceramic disc type capacitor, and the same capacitance can be assured with as small volume as 1/10 or less, and therefore much miniaturization is easy.

When such ceramic dielectric thin film is used, however, it is the fact that conventional disc type ceramic composition can not be used as it is. That is, since a voltage per unit length is loaded 10 times or more than the conventional case, a material having small voltage-dependencies of ceramic dielectric constant and small dissipation factor have become to be needed. Besides, due to recent adoption of direct bonding system onto printed circuit board, such a strong material as is not destroyed by bending of the print circuit board is needed. Further, since in electronics tuner or the like using the laminated ceramic capacitors, the frequencies are shifting to higher band of high sensitivities, those having good high frequency characteristics become necessary also with regard to the laminated ceramic capacitors. Especially, those having characteristic of YD in JIS (Japanese Industrial) standard or characteristic of Y5T in EIA standard are requested by a large number in relation to electronic tuner, and those which have dielectric constant of 3000 or above and tan δ of 2.0% or lower and low equivalent series resistance at frequency band of 1-100 MHz are requested.

DISCLOSURE OF THE INVENTION

Accordingly, this invention provide a dielectric ceramic composition having high dielectric constant, a small dependency of characteristics on voltage, a large bending force, and moreover a small equivalent series resistance in the high frequency region, by having BaTiO₃ as host material and to this adding CaTiO₃ and Sb₂ O₃ to be contained, and further adding either of Nd₂ O₃, La₂ O₃ and Sm₂ O₃ to be contained. Besides, superior characteristics similar to the above-mentioned dielectric ceramic composition is obtainable by having BaTiO₃ as host material and containing CaTiO₃ and Ta₂ O₅ as additives, and further adding Sb₂ O₃ or Pr₆ O₁₁ to be contained.

Furthermore, by adding SiO₂ as to be contained to the above-described dielectric ceramic composition, its strength further increases.

BRIEF EXPLANATION OF THE DRAWING

FIG. 1 is a partially sectional front view of a laminated ceramic capacitor trially made by using the ceramic high dielectric composition of the present invention,

FIG. 2 is a graphs showing frequency characteristic of equivalent series resistance of the laminated ceramic capacitor,

FIG. 3 to FIG. 7 are graphs showing temperature dependent change rates of the same, and

FIG. 8 is a drawing showing an apparatus for examining bending force of the laminated ceramic capacitor made by using the composition of the present invention.

THE BEST MODE FOR EMBODYING THE INVENTION

The present invention is a ceramic high dielectric composition having barium titanate (BaTiO₃) as host material, added with calcium titanate (CaTiO₃), antimony sesquioxide (Sb₂ O₃) and neodymium oxide (Nd₂ O₃), and further if necesary, added with small amount of additives, being belonging to a different group from the conventional compositions, hereinafter it is explained in detail in accordance with the embodiments.

Firstly, to 100 weight parts of BaTiO₃ (of 98% or higher purity), various additives are added and sufficiently mixed in a ball mill. The mixture is added with a small amount of 5% aqueous solution of PVA (polyvinylalcohol), then blended in mortar and filtrated through 30 mesh sieve to be granulated. The granulated powder is put in a die having inner diameter of 13 mm and molded in a size of 13 mm diameter and 0.5 mm thickness by application of a pressure of 1 ton/cm². Also in the similar way, a mold of 47 mm×12.5 mm×1.5 mm size is formed by means of a rectangular die of 47 mm×12.5 mm size. These molds are sintered at 1250°-1400° C. for 1-5 hours. Then, on both face of the disc-shaped sintered body Ag electrodes are provided. The below-mentioned Table 1 shows characteristics of the sintered body obtained by means of various compositions of CaTiO₃, Sb₂ O₃ and Nd₂ O₃ for 100 weight parts of BaTiO₃. Besides, are shown characteristics of sintered body obtained by adding at least one of oxides of Mn, Cr, Fe, Ni and Co. In the table ε₂₅ shows dielectric constant obtained from capacitance measured at 25° C. with 1 KHz AC 1 and tan ε a dielectric loss at that time measured with an AC voltage of effective value 50 V/mm. IR is insulation rsistance measured by direct current (DC) 50 V at 20° C., BDV is rising breakdown voltage value, and AC-V is tan δ value measured with the effective voltage 50 V/mm AC of 1 KHz. Further, TC shows change rate of capacitance measured at -30° C. and +85° C. as reference.

And sintering condition for the above case was 1350° C. for 2 hours.

                                      TABLE 1                                      __________________________________________________________________________                                                             Constant               Sam-                                                                              Additive composition                                 of bending             ple                                                                               (weight parts)        tan δ                                                                       IR     BDV   AC-V                                                                               T C (%)    strength               No.                                                                               CaTiO.sub.3                                                                         Sb.sub.2 O.sub.3                                                                   Nd.sub.2 O.sub.3                                                                   Other ε.sub.25                                                                  (%)                                                                               (Ω · cm)                                                               (kV/mm)                                                                              (%) -30° C.                                                                       +85° C.                                                                      (Kg/cm.sup.2)          __________________________________________________________________________     *1 0    2.5 2.5 --    4048                                                                              1.0                                                                               5 × 10.sup.13                                                                   11    3.5 -20   -46  870                     2 5.0  1.5 1.5 --    3874                                                                              0.8                                                                               6 × 10.sup.13                                                                   18    1.4  -8   -51  1080                    3 10.0 2.5 2.5 --    3891                                                                              0.8                                                                               9 × 10.sup.13                                                                   20    0.9   0   -32  1140                   *4 12.5 1.5 1.5 --    3311                                                                              0.6                                                                               8 × 10.sup.13                                                                   19    1.1  -3   -29  1040                    5 3.0  4.0 1.0 --    4027                                                                              0.7                                                                               9 × 10.sup.13                                                                   13    1.9  15   -65  920                    *6 3.0  0   5.0 --    3833                                                                              1.1                                                                               4 × 10.sup.13                                                                   14    1.4 -13   -28  940                     7 3.0  1.0 5.0 --    3524                                                                              0.9                                                                               7 × 10.sup.13                                                                   16    0.9   5   -30  960                    *8 3.0  3.0 0   --    3019                                                                              0.7                                                                               1.2 × 10.sup.14                                                                 20    1.1  60   -10  1000                   *9 3.0  1.5 6.0 --    2871                                                                              0.4                                                                               9 × 10.sup.13                                                                   11    1.8  -2   -48  890                    *10                                                                               3.0  5.0 1.5 --    3251                                                                              0.4                                                                               8 × 10.sup.13                                                                   15    1.7  20   -20  890                    11 10.0 1.0 5.0 --    3173                                                                              0.6                                                                               6 × 10.sup.13                                                                   12    1.3 -43     4  1100                   12 1.0  4.0 1.0 --    3994                                                                              0.7                                                                               8 × 10.sup.13                                                                   18    0.4  27   -44  900                    13 3.0  1.5 1.5 MnO.sub.2                                                                          0.3                                                                              4432                                                                              0.5                                                                               1 × 10.sup.14                                                                   23    0.7  -3   -36  1020                   *14                                                                               3.0  1.5 1.5 MnO.sub.2                                                                          0.6                                                                              4018                                                                              0.5                                                                               9 × 10.sup.13                                                                   20    0.5 -10   -29  1050                   15 3.0  1.5 1.5 Cr.sub.2 O.sub.3                                                                   0.3                                                                              4391                                                                              1.0                                                                               8 × 10.sup.13                                                                   16    1.2 -15   -21  960                    *16                                                                               3.0  1.5 1.5 Cr.sub.2 O.sub.3                                                                   0.6                                                                              3703                                                                              1.4                                                                               6 × 10.sup.13                                                                   11    1.5 -30   -15  840                    17 3.0  1.5 1.5 Fe.sub.2 O.sub.3                                                                   0.3                                                                              3917                                                                              0.9                                                                               8 × 10.sup.13                                                                   21    1.4 -22   -38  940                    *18                                                                               3.0  1.5 1.5 Fe.sub.2 O.sub.3                                                                   0.6                                                                              3723                                                                              0.7                                                                               4 × 10.sup.13                                                                   19    0.9 -14   -30  970                    19 3.0  1.5 1.5 NiO 0.3                                                                              3841                                                                              1.6                                                                               7 × 10.sup.13                                                                   18    3.1   8   -30  890                    *20                                                                               3.0  1.5 1.5 NiO 0.6                                                                              3629                                                                              2.1                                                                               1 × 10.sup.14                                                                   18    2.0  -2   -19  840                    21 3.0  1.5 1.5 CoO 0.3                                                                              4015                                                                              0.5                                                                               9 × 10.sup.13                                                                   20    1.7  14   -41  1090                   *22                                                                               3.0  1.5 1.5 CoO 0.6                                                                              3140                                                                              0.4                                                                               6 × 10.sup.13                                                                   19    2.0   8   -33  1140                   __________________________________________________________________________      *Comparison example                                                            Remark: Among the additive composition MnO.sub.2 and the like of "other"       shows weight % to the main component.                                    

As is obvious from the Table 1, it is observed that the composition of the present invention is small in capacity change by AC voltage, and strong in bending strength. Since in the conventional composition with addition of BaZrO₃, BaSnO₃ or SRTiO₃ the AC voltage characteristic in tan δ value under 50 V/mm has been so high as about 3-7% and bending strength has been as low as 600-700 Kg/cm², they are considered a very much satisfactory characteristics.

Table 2 shows results of characteristics obtained by trially making laminated ceramic capacitor like the one as shown in FIG. 1 by using the composition of the sample No. 13 of the Table 1, and then examining the characteristics.

FIG. 2 also shows characteristics of capacitors trially made by using conventional representative composition prepared by adding 3 weight parts of BaZrO₃, 0.4 weight part of MgTiO₃ and 0.2 weight parts of MnO₂ to 100 weight parts of BaTiO₃.

In this case, size of the element is 3.07 mm×1.56 mm×0.56 mm. Incidentally, in FIG. 1 numeral 1 designates ceramic dielectric body consisting of the compound of the sample No. 13, 2 palladium electrodes, and 3 terminal electrodes (Ag electrodes). In the Table 2, C and tan δ are values measured with 1 KHz AC 1 V at 20° C., BDVe is rising breakdown voltage. The bending strength is the pressure immediately before destruction of element when the element 4 is held with 2.5 mm span and center part of the element 4 is pressed with a knife of 0.5 mm thick edge as shown in FIG. 8. In FIG. 8, 5 is a sample holding table, 6 is a pressing pin and 7 is a tension gauge with a stop pointer arm.

                                      TABLE 2                                      __________________________________________________________________________                                           Bending                                          C                   T C (%)   strength                                         (pF)                                                                              tan δ (%)                                                                     IRe (%)                                                                             BDVe (kV)                                                                             -30° C.                                                                      +85° C.                                                                      (Kg)                                     __________________________________________________________________________     Composition of                                                                         2240                                                                              0.5  8 × 10.sup.12                                                                 2.4    -3.0 -34.6                                                                               3.5                                      the present                                                                    invention                                                                      (No. 13)                                                                       Conventional                                                                           2320                                                                              2.8  2 × 10.sup.12                                                                 1.6     1.3 -31.2                                                                               1.8                                      composition                                                                    group with                                                                     additive of                                                                    (BaZrO.sub.3)                                                                  __________________________________________________________________________

FIG. 2 shows frequency characteristic of equivalent series resistance of this case. It is clear that as compared with a characteristic A of the capacitor according to the conventional composition, a characteristic B of the capacitor of the present invention trially made by the sample No. 13 has very good characteristic in high frequency range. FIG. 3 also shows temperature change rate of the same capacitor trially made by the present invention.

Nextly, elucidation is made on a second embodiment of the present invention, obtained by that BaTiO₃ is host material and CaTiO₃, Sb₂ O₃ and besides, lanthanum oxide (La₂ O₃) are added to it, and on a third embodiment of the present invention obtained by that BaTiO₃ is host material and CaTiO₃, Sb₂ O₃ and besides samarium oxide (Sm₂ O₃) are added to it. That is, these are a ceramic high dielectric composition formed by adding 1-5 weight parts of CaTiO₃, 1-4 weight parts of Sb₂ O₃ and 1-5 weight parts of La₂ O₃ to 100 weight parts of BaTiO₃, and a ceramic high dielectric composition formed by adding 1-5 weight parts of CaTiO₃, 1-4 weight parts of Sb₂ O₃ and 1-5 weight parts of Sm₂ O₃ to 100 weight parts of BaTiO₃. In these case, 0.01-0.5 wt% of at least one kind of oxides of Mn, Cr, Fe, Ni and Co to the host material may be contained.

The below-mentioned Table 3 and Table 4 show characteristics of sintered bodies obtained for the various additive compositions in the second embodiments; and the condition of preparation is quite the same as that of the embodiments of the above-mentioned first embodiment and the characteristics are measured in the same conditions.

                                      TABLE 3                                      __________________________________________________________________________                                                             Constant               Additive composition                                    of bending             (weight parts)           tan δ                                                                       IR     BDV   AC-V                                                                               T C (%)    strength               No.                                                                               CaTiO.sub.3                                                                         Sb.sub.2 O.sub.3                                                                   La.sub.2 O.sub.3                                                                   Other ε.sub.25                                                                  (%)                                                                               (Ω · cm)                                                               (kV/mm)                                                                              (%) -30° C.                                                                       +85° C.                                                                      (Kg/cm.sup.2)          __________________________________________________________________________     *1 0    2.5 2.0 --    3847                                                                              1.0                                                                               5 × 10.sup.13                                                                   11    3.5  4    -34  840                     2 5.0  1.5 1.5 --    3799                                                                              0.9                                                                               6 × 10.sup.13                                                                   17    1.5 -2    -50  990                     3 10.0 2.5 2.5 --    3681                                                                              0.8                                                                               9 × 10.sup.13                                                                   18    1.0  0    -48  1090                   *4 12.5 1.5 2.0 --    3309                                                                              0.6                                                                               7 × 10.sup.13                                                                   19    1.1 -8    -36  1050                    5 3.0  4.0 1.0 --    3904                                                                              0.8                                                                               9 ×  10.sup.13                                                                  12    1.8 10    -84  940                    *6 3.0  0   5.0 --    3650                                                                              1.1                                                                               6 × 10.sup.13                                                                   11    2.1  3    -42  960                     7 3.0  1.0 5.0 --    3687                                                                              0.9                                                                               7 × 10.sup.13                                                                   13    1.0 18    -70  960                    *8 3.0  3.0 0   --    3019                                                                              0.7                                                                               1.2 × 10.sup.14                                                                 20    1.1 60    -10  1000                   *9 3.0  1.5 6.0 --    2417                                                                              0.4                                                                               8 × 10.sup.13                                                                   10    2.0 -2    -36  910                    *10                                                                               3.0  5.0 1.5 --    3455                                                                              0.6                                                                               7 × 10.sup.13                                                                   15    1.7 16    -27  910                    11 10.0 1.0 5.0 --    3004                                                                              0.7                                                                               5 × 10.sup.13                                                                   10    1.8 -20   -26  960                    12 1.0  4.0 1.0 --    3962                                                                              0.8                                                                               8 × 10.sup.13                                                                   18    0.4 24    -30  900                    13 3.0  1.5 1.0 MnO.sub.2                                                                          0.5                                                                              4296                                                                              0.5                                                                               1 × 10.sup.14                                                                   22    0.7 -3    -34  1110                   *14                                                                               3.0  1.5 1.0 MnO.sub. 2                                                                         0.5                                                                              3971                                                                              0.5                                                                               9 × 10.sup.13                                                                   20    0.5 -7    -29  1090                   15 3.0  1.5 1.0 Cr.sub.2 O.sub.3                                                                   0.3                                                                              4001                                                                              1.0                                                                               8 × 10.sup.13                                                                   16    1.2 -10   -25  970                    *16                                                                               3.0  1.5 1.0 Cr.sub.2 O.sub.3                                                                   0.6                                                                              3602                                                                              0.8                                                                               6 × 10.sup.13                                                                   11    1.6 -26   -14  870                    17 3.0  1.5 1.0 Fe.sub.2 O.sub.3                                                                   0.3                                                                              3999                                                                              0.8                                                                               8 × 10.sup.13                                                                   21    1.4 -30   -19  940                    *18                                                                               3.0  1.5 1.0 Fe.sub.2 O.sub.3                                                                   0.6                                                                              3740                                                                              0.7                                                                               6 × 10.sup.13                                                                   19    0.9 -18   -30  970                    19 3.0  1.5 1.0 NiO 0.3                                                                              3787                                                                              1.4                                                                               7 × 10.sup.13                                                                   18    3.1  8    -36  850                    *20                                                                               3.0  1.5 1.0 NiO 0.6                                                                              3722                                                                              1.1                                                                               1 × 10.sup.14                                                                   18    2.0 -2    -24  800                    21 3.0  1.5 1.0 CoO 0.3                                                                              4032                                                                              0.6                                                                               9 × 10.sup.13                                                                   20    1.7 10    -28  1040                   *22                                                                               3.0  1.5 1.0 CoO 0.6                                                                              3285                                                                              0.5                                                                               6 × 10.sup.13                                                                   19    2.0  4    -30  1090                   __________________________________________________________________________      *Comparison example                                                            Remark: Among the additive composition MnO.sub.2 and the like of "other"       shows weight % to the main component.                                    

                                      TABLE 4                                      __________________________________________________________________________                                                             Constant               Additive composition                                    of bending             (weight parts)           tan δ                                                                        IR    BDV   AC-V                                                                               T C (%)    strength               No.                                                                               CaTiO.sub.3                                                                         Sb.sub.2 O.sub.3                                                                   Sm.sub.2 O.sub.3                                                                   Other ε.sub.25                                                                  (%) (Ω · cm)                                                              (kV/mm)                                                                              (%) -30° C.                                                                       +85° C.                                                                      (Kg/cm.sup.2)          __________________________________________________________________________     *1 0    2.5 2.0 --    4368                                                                              1.3 4 × 10.sup.13                                                                   9    2.9 -12   -43  870                     2 5.0  1.5 1.5 --    4140                                                                              1.0 5 × 10.sup.13                                                                  12    1.4 -4    -46  1040                    3 10.0 2.5 2.5 --    4203                                                                              0.8 7 × 10.sup.13                                                                  18    1.3  2    -28  1100                   *4 12.5 1.5 2.0 --    3108                                                                              0.6 6 × 10.sup.13                                                                  19    1.0  5    -20  1040                    5 3.0  4.5 1.0 --    4270                                                                              0.9 7 × 10.sup.13                                                                  14    1.7 10    -40  920                    *6 3.0  0   5.0 --    3882                                                                              1.1 3 × 10.sup.13                                                                  14    1.6 -10   -25  940                     7 3.0  1.0 5.0 --    3717                                                                              0.9 5 × 10.sup.13                                                                  16    1.1  3    -28  980                    *8 3.0  3.0 0   --    3019                                                                              0.7 12 × 10.sup.14                                                                 20    1.1 60    -10  1000                   *9 3.0  1.5 6.0 --    3104                                                                              0.5 9 × 10.sup.13                                                                   9    1.9  1    -40  900                    *10                                                                               3.0  5.0 1.5 --    3633                                                                              0.6 8 × 10.sup.13                                                                  15    1.7 15    -18  880                    11 10.0 1.0 5.0 --    3591                                                                              0.8 8 × 10.sup.13                                                                  13    1.4 -37     8  1080                   12 1.0  4.0 1.0 --    4087                                                                              1.0 9 × 10.sup.13                                                                  18    0.6 24    -39  900                    13 3.0  1.5 2.0 MnO.sub.2                                                                          0.3                                                                              4602                                                                              0.5 11 × 10.sup.14                                                                 23    0.6 -1    -31  1050                   *14                                                                               3.0  1.5 2.0 MnO.sub.2                                                                          0.6                                                                              4198                                                                              0.5 9 × 10.sup.13                                                                  20    0.5 -8    -28  1080                   15 3.0  1.5 2.0 Cr.sub.2 O.sub.3                                                                   0.3                                                                              4403                                                                              1.0 7 × 10.sup.13                                                                  15    1.2 -15   -24  940                    *16                                                                               3.0  1.5 2.0 Cr.sub.2 O.sub.3                                                                   0.6                                                                              3811                                                                              1.5 5 × 10.sup.13                                                                  11    1.5 -28   -19  870                    17 3.0  1.5 2.0 Fe.sub.2 O.sub.3                                                                   0.3                                                                              4029                                                                              1.1 8 × 10.sup.13                                                                  18    0.9 -18   -32  940                    *18                                                                               3.0  1.5 2.0 Fe.sub.2 O.sub.3                                                                   0.6                                                                              3755                                                                              0.8 5 × 10.sup.13                                                                  17    0.7 -9    -28  980                    19 3.0  1.5 2.0 NiO 0.3                                                                              3910                                                                              1.5 8 × 10.sup.13                                                                  17    2.8 11    -27  870                    *20                                                                               3.0  1.5 2.0 NiO 0.6                                                                              3723                                                                              2.2 1 × 10.sup.14                                                                  17    1.8  1    -16  850                    21 3.0  1.5 2.0 CoO 0.3                                                                              4296                                                                              0.6 9 × 10.sup.13                                                                  20    1.7 17    -37  1120                   *22                                                                               3.0  1.5 2.0 CoO 0.6                                                                              3509                                                                              0.5 6 × 10.sup.13                                                                  18    2.0 11    -30  1166                   __________________________________________________________________________      *Comparison example                                                            Remark: Among the additive composition MnO.sub.2 and the like of "other"       shows weight % to the main component.                                    

Nextly, elucidation is made on a fourth embodiment of the present invention wherein BaTiO₃ is a host material and CaTiO₃, Ta₂ O₅ and further antimony sesquioxide (Sb₂ O₃) are added to it, and a fifth embodiment of the present invention wherein BaTiO₃ is a host material and CaTiO₃, Ta₂ O₅ and further praseodymium oxide Pr₆ O₁₁ are added to it. That is, these are a ceramic high dielectric composition formed by adding 1-5 weight parts of CaTiO₃, 1-4 weight parts of Ta₂ O₅ and 1-5 weight parts of Sb₂ O₃ to 100 weight parts of BaTiO₃, and a ceramic high dielectric composition formed by adding 1-5 weight parts of CaTiO₃, 1-4 weight parts of Ta₂ O₅ and 1-4 weight parts of Pr₆ O₁₁ to 100 weight parts of BaTiO₃. Also in these cases, 0.01-0.5% by weight of at least one kind of oxide of Mn, Cr, Fe, Ni and Co to the host material may be contained.

The below-mentioned Table 5 and Table 6 show characteristics of sintered bodies obtained for the various additive compositions in the fourth and fifth embodiments, and the conditions are quite the same as that of the embodiment of the above-mentioned first embodiment and the characteristics are measured under the same conditions.

                                      TABLE 5                                      __________________________________________________________________________                                                             Constant               Additive composition                                    of bending             (weight parts)            tan δ                                                                        IR   BDV   AC-V                                                                               T C (%)    strength               No.                                                                               CaTiO.sub.3                                                                         Ta.sub.2 O.sub.5                                                                   Sb.sub.2 O.sub.3                                                                   Other ε.sub.25                                                                   (%) (Ω · cm)                                                             (kV/mm)                                                                              (%) -30° C.                                                                       +85° C.                                                                      (Kg/cm.sup.2)          __________________________________________________________________________     *1 0    2.5 1.5 --    3493                                                                               1.0 5 × 10.sup.13                                                                 10    3.0 -15   -52   950                    2 3.0  2.0 1.5 --    3043                                                                               0.7 4 × 10.sup.13                                                                 12    2.7 0     -28.2                                                                                930                    3 3.0  4.0 1.0 --    3524                                                                               1.2 3 × 10.sup.13                                                                 11    1.0 -2.0  -35.3                                                                                970                    4 3.0  5.0 5.0 --    4073                                                                               0.9 7 × 10.sup.13                                                                 12    1.6 -8.5  -39.4                                                                               1030                    5 10.0 2.0 1.0 --    2830                                                                               0.8 6 ×  10.sup.13                                                                16    1.2 -6.2  -40.3                                                                                950                   *6 12.5 2.0 1.5 --    2127                                                                               0.8 9 × 10.sup.13                                                                 19    1.8 -23.4 -65.8                                                                                930                   *7 3.0  0   5.0 --    Not be                                                                             --  --   --    --  --    --   --                                           sin-                                                                           tered                                                     8 2.0  1.0 5.0 --    3346                                                                               0.2 3 × 10.sup.13                                                                 12    1.9 -6.4  -38.4                                                                                740                   *9 3.0  2.0 0   --    4453                                                                               1.3 9 × 10.sup.13                                                                 13    2.0 -7.4  -75.4                                                                                860                   *10                                                                               3.0  5.0 6.0 --    4528                                                                               1.5 2 × 10.sup.13                                                                 17    1.8 -60.4 -32.4                                                                               1020                   *11                                                                               3.0  6.0 1.5 --    1870                                                                               0.6 6 × 10.sup.13                                                                 15    2.5 -54.5 -30.4                                                                                980                   12 10.0 1.0 5.0 --    2982                                                                               0.7 4 × 10.sup.13                                                                 18    1.6 -36   -30  1000                   13 1.0  10.0                                                                               1.0 --    3573                                                                               0.9 5 × 10.sup.13                                                                 19    1.8 -45   -28   980                   14  3.0 2.0 1.5 MnO.sub.2                                                                          0.3                                                                              3973                                                                               0.8 8 × 10.sup.13                                                                 15    1.2 -3.2  -30  1100                   *15                                                                               3.0  2.0 1.5 MnO.sub.2                                                                          0.6                                                                              3465                                                                               0.6 8 × 10.sup.13                                                                 14    1.0 -7.5  -27  1050                   16 3.0  2.0 1.5 Cr.sub.2 O.sub.3                                                                   0.3                                                                              3326                                                                               0.9 9 × 10.sup.13                                                                 17    1.5 -6    -27  1120                   *17                                                                               3.0  2.0 1.5 Cr.sub.2 O.sub.3                                                                   0.6                                                                              2178                                                                               0.4 6 × 10.sup.13                                                                 18    0.9 -8    -26  1220                   18 3.0  2.0 1.5 Fe.sub.2 O.sub.3                                                                   0.3                                                                              3289                                                                               0.8 5 × 10.sup.13                                                                 16    1.8 -13   -34  1070                   19 3.0  2.0 1.5 Fe.sub.2 O.sub.3                                                                   0.6                                                                              3065                                                                               0.7 7 × 10.sup.13                                                                 15    1.6 -17   -30  1050                   20 3.0  2.0 1.5 NiO 0.3                                                                              3342                                                                               0.5 4 × 10.sup.13                                                                 13    1.2 -15   -38  1010                   21 3.0  2.0 1.5 NiO 0.6                                                                              3384                                                                               0.7 2 × 10.sup.13                                                                 17    1.4 -20   -40  1080                   22 3.0  2.0 1.5 CoO 0.3                                                                              3201                                                                               0.9 6 × 10.sup.13                                                                 11    2.0 -10   -35  1040                   23 3.0  2.0 1.5 CoO 0.6                                                                              3052                                                                               0.6 5 × 10.sup.13                                                                 13    1.8 -15   -33   960                   __________________________________________________________________________      *Comparison example                                                            Remark: Among the additive composition MnO.sub.2 and the like of "other"       shows weight % to the main component.                                    

                                      TABLE 6                                      __________________________________________________________________________                                                             Constant               Additive composition                                    of bending             (weight parts)            tan δ                                                                        IR   BDV   AC-V                                                                               T C (%)    strength               No.                                                                               CaTiO.sub.3                                                                         Ta.sub.2 O.sub.5                                                                   Pr.sub.6 O.sub.11                                                                  Other ε.sub.25                                                                   (%) (Ω · cm)                                                             (kV/mm)                                                                              (%) -30° C.                                                                       +85° C.                                                                      (Kg/cm.sup.2)          __________________________________________________________________________     *1 0    2.5 1.5 --    3760                                                                               1.2 2 × 10.sup.13                                                                 11    3.5 -10   -35  970                     2 3.0  2.0 1.5 --    3476                                                                               0.7 2 × 10.sup.13                                                                 14    1.3 -20   -31  1030                    3 3.0  4.0 1.0 --    3698                                                                               1.1 5 × 10.sup.13                                                                 12    1.9 -3    -23  990                     4 3.0  5.0 5.0 --    2740                                                                               0.7 7 × 10.sup.13                                                                 13    1.4  4    -44  850                     5 10.0 2.0 1.0 --    2978                                                                               0.9 2 ×  10.sup.13                                                                14    1.5 -5    -33  980                    *6 12.5 2.0 1.0 --    2484                                                                               0.6 8 × 10.sup.13                                                                 17    1.2 -2    -24  1020                   *7 3.0  0   5.0 --    Not be                                                                             --  --   --    --  --    --   --                                           sin-                                                                           tered                                                     8 2.0  1.0 5.0 --    3597                                                                               1.0 6 × 10.sup.13                                                                 14    1.7 -3    -42  980                    *9 3.0  2.0 0   --    3324                                                                               0.9 3 × 10.sup.13                                                                 11    1.6 -10   -24  900                    *10                                                                               3.0  5.0 6.0 --    2127                                                                               0.7 7 × 10.sup.13                                                                 10    1.4  8    -64  630                    *11                                                                               3.0  6.0 1.5 --    2874                                                                               0.8 6 × 10.sup.13                                                                 15    1.5  3    -54  620                    12 10.0 1.0 5.0 --    3079                                                                               0.7 4 × 10.sup.13                                                                 16    1.3 -2    -41  1010                   13 1.0  10.0                                                                               1.0 --    3522                                                                               1.1 8 × 10.sup.13                                                                 16    1.9 -3    -35  930                    14 3.0  2.0 1.5 MnO.sub.2                                                                          0.3                                                                              3381                                                                               0.8 9 × 10.sup.13                                                                 19    1.6 -4    -29  1190                   *15                                                                               3.0  2.0 1.5 MnO.sub.2                                                                          0.6                                                                              3125                                                                               0.6 5 × 10.sup.13                                                                 20    1.2 -6    -24  1100                   16 3.0  2.0 1.5 Cr.sub.2 O.sub.3                                                                   0.3                                                                              3134                                                                               0.7 8 × 10.sup.13                                                                 21    1.6 -2    -33  1250                   *17                                                                               3.0  2.0 1.5 Cr.sub.2 O.sub.3                                                                   0.6                                                                              2838                                                                               0.5 7 × 10.sup.13                                                                 18    1.0 -6    -29  1040                   18 3.0  2.0 1.5 Fe.sub.2 O.sub.3                                                                   0.3                                                                              3254                                                                               1.0 9 × 10.sup.13                                                                 20    1.9 -13   -33  1080                   *19                                                                               3.0  2.0 1.5 Fe.sub.2 O.sub.3                                                                   0.6                                                                              3056                                                                               0.9 7 × 10.sup.13                                                                 18    1.4 -15   -29  1000                   20 3.0  2.0 1.5 NiO 0.3                                                                              3340                                                                               0.7 3 × 10.sup.13                                                                 19    1.4 -8    -35  1050                   *21                                                                               3.0  2.0 1.5 NiO 0.6                                                                              3276                                                                               1.8 5 × 10.sup.13                                                                 17    3.5 -2    -48  980                    22 3.0  2.0 1.5 CoO 0.3                                                                              3115                                                                               1.1 2 × 10.sup.13                                                                 18    1.6 -12   -32  970                    *23                                                                               3.0  2.0 1.5 CoO 0.6                                                                              3048                                                                               1.6 2 × 10.sup.13                                                                 14    2.2 -10   -44  990                    __________________________________________________________________________      *Comparison example                                                            Remark: Among the additive composition MnO.sub.2 and the like of "other"       shows weight % to the main component.                                    

As is obvious from the Table 3-Table 6, it is observed that also for the compositions of the second embodiments through fifth embodiments, like the first embodiment, the dielectric constant is large, capacity change depending on AC voltage is small and bending strength is great. Hereupon, though in the second through fifth embodiments, the only such cases have been illustrated that as shown in Table 3 to Table 6 each one kind of MnO₂, Cr₂ O₃, Fe₂ O₃, NiO and CoO as the additive composition has been included to the host material, but the inventors confirmed that similar effect is obtainable even when two kinds or more of these oxides are combined and included. In that case, it is similar to the above-mentioned embodiments that when the additive amount to the host material is included exceeding 0.5 weight % the characteristic of ε₂₅ is deteriorated. Also, the inventor confirmed that by inclusion of 0.01 weight % or more (0.5 weight % or smaller) of at least one kind of oxide of Mn, Cr, Fe, Ni and Co to the host material, the compositions of the above-mentioned second through fifth embodiments have the similar effect as the characteristics shown in the Table 3 through Table 6. Also, composition of the samples No. 13 of the Table 3 and Table 4 and composition of sample No. 14 of the Table 5, and composition of sample 15 of Table 6 are respectively used and the above-mentioned laminated ceramic capacitors were trially made, and their characteristics were examined, and the results are shown on the below-mentioned Table 7. In this case the sizes of the element were similar to the embodiment of the first embodiment, and the characteristics were measured also under the same conditions.

                                      TABLE 7                                      __________________________________________________________________________                                       Bending                                              C  tan δ                                                                       IRe  BDVe                                                                               T C (%)    strength                                             (pF)                                                                              (%)                                                                               (Ω)                                                                           (kV)                                                                               -30° C.                                                                       +85° C.                                                                      (Kg)                                         __________________________________________________________________________     Second  2240                                                                              0.5                                                                               8 × 10.sup.12                                                                 2.4 -3.0  -34.6                                                                               3.7                                          embodiment                                                                     Sample No. 13                                                                  of Table 3                                                                     Third   2410                                                                              0.5                                                                               8 × 10.sup.12                                                                 2.3 -1.0  -29.4                                                                               3.4                                          embodiment                                                                     Sample No. 13                                                                  of Table 4                                                                     Fourth  2250                                                                              0.8                                                                               5 × 10.sup.12                                                                 2.0 -2.5  -30.5                                                                               3.3                                          embodiment                                                                     Sample No. 14                                                                  of Table 5                                                                     Fifth   2265                                                                              0.9                                                                               6 × 10.sup.12                                                                 2.1 -1.4  -31.5                                                                               3.4                                          embodiment                                                                     Sample No. 15                                                                  of Table 6                                                                     __________________________________________________________________________

Frequency characteristic of the equivalent series resistance in this case is, like the above-described first embodiment, was confirmed as very good characteristics of high frequency in comparison with the characteristic A of the capacitor of the conventional component (composition of the group with additive of the above-described BaZrO₃).

FIG. 4 through FIG. 7 similarly show temperature change ratio of capacitance of the capacitors trially made with the compositions of the second through fifth embodiments.

Nextly, explains are made on sixth through tenth embodiments of the present invention which are to be obtained by adding SiO₂ further to the first to fifth compounds of the present invention. That is, these are ceramic high dielectric compounds made by adding 1-5 weight parts of CaTiO₃, 1-4 weight parts of Sb₂ O₃, 1-5 weight parts of Nd₂ O₃ and 0.1-1 weight parts of SiO₂ to 100 weight parts of BaTiO₃, ceramic high dielectric compounds made by adding 1-5 weight parts of CaTiO₃, 1-4 weight parts of Sb₂ O₃, 1-5 weight parts of La₂ O₃ and 0.1-1 weight parts of SiO₂ to 1-5 weight parts of BaTiO₃, ceramic high dielectric compounds made by adding 1-5 weight parts of CaTiO₃, 1-4 weight parts of Sb₂ O₃, 1-5 weight parts of Sm₂ O₃ and 0.1-1 weight parts of SiO₂ to 100 weight parts of BaTiO₃, ceramic high dielectric compounds made by adding 1-5 weight parts of CaTiO₃, 1-4 weight parts of Ta₂ O₅ 1-5 weight parts of Sb₂ O₃ and 0.1-1 weight parts of SiO₂ to 100 weight parts of BaTiO₃ and ceramic high dielectric compounds made by adding 1-5 weight parts of CaTiO₃, 1-4 weight parts of Ta₂ O₃, 1-5 weight parts of Pr₆ O₁₁ and 0.1-1 weight parts of SiO₂ to 100 weight parts of BaTiO₃. In these cases, at least one kind of oxides of Mn, Cr, Fe, Ni and Co may be included at a rate of 0.01-0.5 wt% to the host material. The below-mentioned Tables 8 through Table 12 show results of examinations of characteristics of laminated ceramic capacitors which are trially made for the variously added compositions of the sixth through tenth embodiments. In this case sizes of elements are similar to the first embodiment. The bending force was pressures which was immediately before the element destruction when the element 4 was supported with 2.0 mm span and the central part of the element 4 was pressed with a knife of 0.5 mm edge width as shown in FIG. 12. C and tan δ and IRe were measured under the same condition as that of the embodiment of FIG. 1.

                                      TABLE 8                                      __________________________________________________________________________                              Bending                                               Additive composition (weight parts)                                                                     strength                                                                            Capacitance                                                                           tan δ                                                                       IR                                     No.                                                                               CaTiO.sub.3                                                                         Sb.sub.2 O.sub.3                                                                   Nd.sub.2 O.sub.3                                                                   SiO.sub.2                                                                         Other (Kg) (pF)   (%)                                                                               (Ω)                              __________________________________________________________________________     *1 0    2.5 2.5 0.5                                                                               --    2.0  2412   1.9                                                                               10.sup.12                               2 5.   1.5 1.5 0.5                                                                               --    2.5  2345   1.7                                                                               10.sup.12                               3 10.0 2.5 2.5 0.3                                                                               --    2.6  2380   1.7                                                                               10.sup.12                              *4 12.5 1.5 1.5 0.5                                                                               --    2.3  2011   1.4                                                                               10.sup.12                               5 3.0  4.0 1.0 0.3                                                                               --    2.3  2421   1.4                                                                               10.sup.12                              *6 3.0  0   5.0 0.7                                                                               --    2.4  2325   2.1                                                                               10.sup.12                               7 3.0  1.0 5.0 0.7                                                                               --    2.4  2287   1.8                                                                               10.sup.12                              *8 3.0  1.0 5.0 1.1                                                                               --    2.0  1633   1.9                                                                               10.sup.12                              *9 3.0  3.0 0   0.5                                                                               --    2.5  1946   1.6                                                                               10.sup.12                              *10                                                                               3.0  1.5 6.0 0.5                                                                               --    2.2  1819   1.2                                                                               10.sup.12                              *11                                                                               3.0  5.0 1.5 0.5                                                                               --    2.2  2014   1.2                                                                               10.sup.12                              *12                                                                               3.0  1.0 1.5 0  --    2.6  2400   1.5                                                                               10.sup.12                              13 3.0  1.5 1.0 1.0                                                                               --    2.3  2217   1.8                                                                               10.sup.12                              14 3.0  1.5 4.0 0.1                                                                               --    2.7  2131   1.4                                                                               10.sup.12                              15 3.0  1.5 1.5 0.1                                                                               --    2.7  2333   1.5                                                                               10.sup.12                              16 3.0  1.5 1.5 0.3                                                                               --    2.8  2437   1.6                                                                               10.sup.12                              17 3.0  1.5 1.5 0.5                                                                               --    2.7  2378   1.6                                                                               10.sup.12                              18 3.0  1.5 1.5 0.7                                                                               --    2.6  2285   1.6                                                                               10.sup.12                              19 3.0  1.5 1.5 1.0                                                                               --    2.6  2194   1.6                                                                               10.sup.12                              20 3.0  1.5 1.5 0.5                                                                               --    2.5  2209   1.4                                                                               10.sup.12                              21 3.0  1.5 1.5 0.3                                                                               MnO.sub.2                                                                          0.3                                                                              2.8  2396   1.5                                                                               10.sup.12                              *22                                                                               3.0  1.5 1.5 0.3                                                                               MnO.sub.2                                                                          0.6                                                                              2.6  2127   1.5                                                                               10.sup.12                              23 3.0  1.5 1.5 0.3                                                                               Cr.sub.2 O.sub.3                                                                   0.3                                                                              2.7  2328   1.6                                                                               10.sup.12                              *24                                                                               3.0  1.5 1.5 0.3                                                                               Cr.sub.2 O.sub.3                                                                   0.6                                                                              2.4  2164   1.7                                                                               10.sup.12                              25 3.0  1.5 1.5 0.3                                                                               Fe.sub.2 O.sub.3                                                                   0.3                                                                              2.5  2287   1.8                                                                               10.sup. 12                             *26                                                                               3.0  1.5 1.5 0.3                                                                               Fe.sub.2 O.sub.3                                                                   0.6                                                                              2.6  2215   1.6                                                                               10.sup.12                              27 3.0  1.5 1.5 0.3                                                                               NiO 0.3                                                                              2.4  2304   2.0                                                                               10.sup.12                              *28                                                                               3.0  1.5 1.5 0.3                                                                               NiO 0.6                                                                              2.3  2173   1.8                                                                               10.sup.12                              29 3.0  1.5 1.5 0.3                                                                               CoO 0.3                                                                              2.5  2389   1.6                                                                               10.sup.12                              *30                                                                               3.0  1.5 1.5 0.3                                                                               CoO 0.6                                                                              2.6  2332   1.4                                                                               10.sup.12                              __________________________________________________________________________      *Comparison example                                                            Remark: Among the additive composition MnO.sub.2 and the like of "other"       shows weight % to the main component.                                    

                                      TABLE 9                                      __________________________________________________________________________                              Bending                                                                             Capaci-                                          Additive composition (weight parts)                                                                     strength                                                                            tance                                                                               tan δ                                                                       IR                                       No.                                                                               CaTiO.sub.3                                                                         Sb.sub.2 O.sub.3                                                                   La.sub.2 O.sub.3                                                                   SiO.sub.2                                                                         Other (Kg) (pF) (%)                                                                               (Ω)                                __________________________________________________________________________     *1 0    2.5 2.0 0.5                                                                               --    1.9  2139 1.7                                                                               10.sup.12                                 2 15.0 1.5 1.5 0.5                                                                               --    2.3  2102 1.7                                                                               10.sup.12                                 3 10.0 2.5 2.5 0.5                                                                               --    2.5  2070 1.6                                                                               10.sup.12                                *4 2.5  1.5 2.0 0.5                                                                               --    2.4  1871 1.4                                                                               10.sup.12                                 5 3.0  4.0 1.0 0.3                                                                               --    2.2  2113 1.6                                                                               10.sup.12                                *6 3.0  0   5.0 0.5                                                                               --    2.3  2065 1.9                                                                               10.sup.12                                 7 3.0  1.0 5.0 0.5                                                                               --    2.3  2072 1.7                                                                               10.sup.12                                *8 3.0  3.0 0   0.5                                                                               --    2.4  1694 1.5                                                                               10.sup.12                                *9 3.0  1.5 6.0 0.5                                                                               --    2.3  1336 1.3                                                                               10.sup.12                                *10                                                                               3.0  5.0 1.5 0.5                                                                               --    2.3  1986 1.4                                                                               10.sup.12                                *11                                                                               3.0  1.0 5.0 1.1                                                                               --    2.5  1595 1.6                                                                               10.sup.12                                *12                                                                               3.0  1.5 1.0 0  --    2.5  2162 1.5                                                                               10.sup.12                                13 0.0  1.0 5.0 0.5                                                                               --    2.4  1624 1.4                                                                               10.sup.12                                14 1.0  4.0 1.0 0.5                                                                               --    2.3  2153 1.6                                                                               10.sup.12                                15 7.0  1.5 1.0 0.5                                                                               --    2.4  2061 1.6                                                                               10.sup.12                                16 3.0  1.5 1.0 0.1                                                                               --    2.6  2142 1.5                                                                               10.sup.12                                17 3.0  1.5 1.0 0.3                                                                               --    2.6  2128 1.5                                                                               10.sup.12                                18 3.0  1.5 1.0 0.5                                                                               --    2.7  2090 1.4                                                                               10.sup.12                                19 3.0  1.5 1.0 0.7                                                                               --    2.8  2012 1.4                                                                               10.sup.12                                20 3.0  1.5 1.0 1.0                                                                               --    2.8  1943 1.4                                                                               10.sup.12                                21 3.0  1.5 1.0 0.5                                                                               MnO.sub.2                                                                          0.3                                                                              2.8  2256 1.6                                                                               10.sup.12                                22 3.0  1.5 1.0 0.5                                                                               MnO.sub.2                                                                          0.6                                                                              2.6  2099 1.6                                                                               10.sup.12                                23 3.0  1.5 1.0 0.5                                                                               Cr.sub.2 O.sub.3                                                                   0.3                                                                              2.4  2108 1.8                                                                               10.sup.12                                24 3.0  1.5 1.0 0.5                                                                               Cr.sub.2 O.sub.3                                                                   0.6                                                                              2.0  2021 1.6                                                                               10.sup.12                                25 3.0  1.5 1.0 0.5                                                                               Fe.sub.2 O.sub.3                                                                   0.3                                                                              2.4  2130 1.6                                                                               10.sup.12                                26 3.0  1.5 1.0 0.5                                                                               Fe.sub.2 O.sub.3                                                                   0.6                                                                              2.5  2025 1.6                                                                               10.sup.12                                27 3.0  1.5 1.0 0.5                                                                               NiO 0.3                                                                              2.0  2088 2.0                                                                               10.sup.12                                28 3.0  1.5 1.0 0.5                                                                               NiO 0.6                                                                              1.9  2019 1.8                                                                               10.sup.12                                29 3.0  1.5 1.0 0.5                                                                               CoO 0.3                                                                              2.5  2104 1.4                                                                               10.sup.12                                30 3.0  1.5 1.0 0.5                                                                               CoO 0.6                                                                              2.6  1692 1.2                                                                               10.sup.12                                __________________________________________________________________________      *Comparison example                                                            Remark: Among the additive composition MnO.sub.2 and the like of "other"       shows weight % to the main component.                                    

                                      TABLE 10                                     __________________________________________________________________________                              Bending                                                                             Capaci-                                          Additive composition (weight parts)                                                                     strength                                                                            tance                                                                               tan δ                                                                       IR                                       No.                                                                               CaTiO.sub.3                                                                         Sb.sub.2 O.sub.3                                                                   Sm.sub.2 O.sub.3                                                                   SiO.sub.2                                                                         Other (Kg) (pF) (%)                                                                               (Ω)                                __________________________________________________________________________     *1 0    2.5 2.0 0.5                                                                               --    2.1  2345 2.0                                                                               10.sup.12                                 2 5.0  1.5 1.5 0.5                                                                               --    2.4  2198 1.7                                                                               10.sup.12                                 3 10.0 2.5 2.5 0.5                                                                               --    2.6  2229 1.6                                                                               10.sup.12                                *4 12.5 1.5 2.0 0.5                                                                               --    2.5  1481 1.4                                                                               10.sup.12                                 5 3.0  4.0 1.0 0.3                                                                               --    2.3  2245 1.7                                                                               10.sup.12                                *6 3.0  0   5.0 0.3                                                                               --    2.3  2063 1.9                                                                               10.sup.12                                 7 3.0  1.0 5.0 0.3                                                                               --    2.5  2024 1.7                                                                               10.sup.12                                *8 3.0  3.0 0   0.3                                                                               --    2.6  1402 1.6                                                                               10.sup.12                                 9 3.0  1.5 6.0 0.3                                                                               --    2.4  1487 1.3                                                                               10.sup.12                                10 3.0  5.0 1.5 0.5                                                                               --    2.4  1911 1.6                                                                               10.sup.12                                11 3.0  1.0 5.0 1.1                                                                               --    2.7  1874 1.7                                                                               10.sup.12                                12 3.0  1.5 2.0 0  --    2.4  2168 1.6                                                                               10.sup.12                                13 10.0 1.0 5.0 0.5                                                                               --    2.6  1903 1.6                                                                               10.sup.12                                14 1.0  4.0 2.0 0.5                                                                               --    2.4  2119 1.8                                                                               10.sup.12                                15 7.0  1.5 2.0 0.3                                                                               --    2.5  2142 1.6                                                                               10.sup.12                                16 3.0  1.5 2.0 0.1                                                                               --    2.5  2142 1.6                                                                               10.sup.12                                17 3.0  1.5 2.0 0.3                                                                               --    2.7  2128 1.6                                                                               10.sup.12                                18 3.0  1.5 2.0 0.5                                                                               --    2.7  2103 1.5                                                                               10.sup.12                                19 3.0  1.5 2.0 0.7                                                                               --    2.6  2044 1.5                                                                               10.sup.12                                20 3.0  1.5 2.0 1.0                                                                               --    2.6  1857 1.5                                                                               10.sup.12                                21 3.0  1.5 2.0 0.3                                                                               MnO.sub.2                                                                          0.3                                                                              2.5  2433 1.2                                                                               10.sup.12                                22 3.0  1.5 2.0 0.3                                                                               MnO.sub.2                                                                          0.6                                                                              2.5  2186 1.2                                                                               10.sup.12                                23 3.0  1.5 2.0 0.3                                                                               Cr.sub.2 O.sub.3                                                                   0.3                                                                              2.4  2383 1.8                                                                               10.sup.12                                24 3.0  1.5 2.0 0.3                                                                               Cr.sub.2 O.sub.3                                                                   0.6                                                                              2.3  1991 2.3                                                                               10.sup.12                                25 3.0  1.5 2.0 0.3                                                                               Fe.sub.2 O.sub.3                                                                   0.3                                                                              2.4  2074 1.9                                                                               10.sup.12                                26 3.0  1.5 2.0 0.3                                                                               Fe.sub.2 O.sub.3                                                                   0.6                                                                              2.5  1884 1.6                                                                               10.sup.12                                27 3.0  1.5 2.0 0.3                                                                               NiO 0.3                                                                              2.3  2036 2.0                                                                               10.sup.12                                28 3.0  1.5 20  0.3                                                                               NiO 0.6                                                                              2.3  1985 2.8                                                                               10.sup.12                                29 3.0  1.5 20  0.3                                                                               CoO 0.3                                                                              2.7  2345 1.4                                                                               10.sup.12                                30 3.0  1.5 20  0.3                                                                               CoO 0.6                                                                              2.7  1768 1.2                                                                               10.sup.12                                __________________________________________________________________________      *Comparison example                                                            Remark: Among the additive composition MnO.sub.2 and the like of "other"       shows weight % to the main component.                                    

                                      TABLE 11                                     __________________________________________________________________________                              Bending                                                                             Capaci-                                          Additive composition (weight parts)                                                                     strength                                                                            tance                                                                               tan δ                                                                       IR                                       No.                                                                               CaTiO.sub.3                                                                         Ta.sub.2 O.sub.5                                                                   Sb.sub.2 O.sub.3                                                                   SiO.sub.2                                                                         Other (Kg) (pF) (%)                                                                               (Ω)                                __________________________________________________________________________     *1 0    3.0 3.0 0.5                                                                               --    2.1  2572 2.0                                                                               10.sup.12                                 2 1.0  3.0 5.0 0.7                                                                               --    2.2  2456 1.8                                                                               10.sup.12                                 3 3.0  5.0 3.0 1.0                                                                               --    2.3  2390 1.7                                                                               10.sup.12                                 4 10.0 3.0 5.0 0.5                                                                               --    2.5  2115 1.8                                                                               10.sup.12                                *5 11.0 3.0 3.0 0.3                                                                               --    2.4  1765 1.8                                                                               10.sup.12                                *6 3.0  0   3.0 0.5                                                                               --    Not be sintered                                        7 3.0  1.0 3.0 0.7                                                                               --    2.4  2387 1.8                                                                               10.sup.12                                 8 3.0  3.0 1.0 1.0                                                                               --    2.5  2470 1.7                                                                               10.sup.12                                 9 3.0  5.0 5.0 0.5                                                                               --    2.3  2684 1.6                                                                               10.sup.12                                *10                                                                               3.0  6.0 5.0 0.7                                                                               --    2.4  2890 1.8                                                                               10.sup.12                                *11                                                                               3.0  5.0 0   0.3                                                                               --    2.1  1623 1.8                                                                               10.sup.12                                *12                                                                               3.0  2.0 1.0 0  --    1.8  2105 2.0                                                                               10.sup.12                                13 3.0  3.0 3.0 0.3                                                                               --    2.2  2284 1.9                                                                               10.sup.12                                14 3.0  3.0 5.0 0.5                                                                               --    2.4  2673 1.8                                                                               10.sup.12                                *15                                                                               3.0  1.0 6.0 1.0                                                                               --    2.2  1686 1.8                                                                               10.sup.12                                16 3.0  1.0 3.0 0  --    1.8  2240 1.9                                                                               10.sup.12                                17 3.0  1.0 3.0 0.1                                                                               --    2.1  2230 1.8                                                                               10.sup.12                                18 3.0  1.0 3.0 0.3                                                                               --    2.2  2238 1.7                                                                               10.sup.12                                19 3.0  1.0 3.0 0.5                                                                               --    2.3  2170 1.8                                                                               10.sup.12                                20 3.0  1.0 3.0 1.0                                                                               --    2.4  2082 1.8                                                                               10.sup.12                                *21                                                                               3.0  1.0 3.0 1.1                                                                               --    2.3  1671 1.7                                                                               10.sup.12                                22 3.0  1.0 3.0 0.5                                                                               MnO 0.3                                                                              2.2  2173 1.6                                                                               10.sup.12                                *23                                                                               3.0  1.0 3.0 0.5                                                                               MnO 0.6                                                                              2.4  2108 1.5                                                                               10.sup.12                                24 3.0  1.0 3.0 0.5                                                                               Cr.sub.2 O.sub.3                                                                   0.3                                                                              2.3  2132 1.7                                                                               10.sup.12                                *25                                                                               3.0  1.0 3.0 0.5                                                                               Cr.sub.2 O.sub.3                                                                   0.6                                                                              2.2  2191 1.6                                                                               10.sup.12                                26 3.0  1.0 3.0 0.5                                                                               Fe.sub.2 O.sub.3                                                                   0.3                                                                              2.3  2290 1.7                                                                               10.sup.12                                *27                                                                               3.0  1.0 3.0 0.5                                                                               Fe.sub.2 O.sub.3                                                                   0.6                                                                              2.4  2052 1.6                                                                               10.sup.12                                28 3.0  1.0 3.0 0.5                                                                               NiO 0.3                                                                              2.5  2227 1.6                                                                               10.sup.12                                *29                                                                               3.0  1.0 3.0 0.5                                                                               NiO 0.6                                                                              2.3  2190 1.5                                                                               10.sup.12                                30 3.0  1.0 3.0 0.5                                                                               CoO 0.3                                                                              2.2  2182 1.5                                                                               10.sup.12                                *31                                                                               3.0  1.0 3.0 0.5                                                                               CoO 0.6                                                                              2.1  2133 1.5                                                                               10.sup.12                                __________________________________________________________________________      *Comparison example                                                            Remark: Among the additive composition MnO.sub.2 and the like of "other"       shows weight % to the main component.                                    

                                      TABLE 12                                     __________________________________________________________________________                              Bending                                                                             Capaci-                                          Additive composition (weight parts)                                                                     strength                                                                            tance                                                                               tan δ                                                                       IR                                       No.                                                                               CaTiO.sub.3                                                                         Ta.sub.2 O.sub.5                                                                   Pr.sub.6 O.sub.11                                                                  SiO.sub.2                                                                         Other (Kg) (pF) (%)                                                                               (Ω)                                __________________________________________________________________________     *1 0    3.0 3.0 0.5                                                                               --    2.2  2473 1.8                                                                               10.sup.12                                 2 1.0  3.0 5.0 0.7                                                                               --    2.3  2387 1.8                                                                               10.sup.12                                 3 3.0  5.0 3.0 1.0                                                                               --    2.3  2295 1.7                                                                               10.sup.12                                 4 0.0  3.0 5.0 0.5                                                                               --    2.4  2163 1.6                                                                               10.sup.12                                *5 1.0  3.0 3.0 0.3                                                                               --    2.4  1650 1.5                                                                               10.sup.12                                *6 3.0  0   3.0 0.5                                                                               --         --   -- --                                        7 3.0  1.0 3.0 0.7                                                                               --    2.3  2365 1.5                                                                               10.sup.12                                 8 3.0  3.0 1.0 1.0                                                                               --    2.5  2490 1.7                                                                               10.sup.12                                 9 3.0  5.0 5.0 0.5                                                                               --    2.2  2669 1.9                                                                               10.sup.12                                *10                                                                               3.0  6.0 5.0 0.7                                                                               --    2.4  2757 1.8                                                                               10.sup.12                                *11                                                                               3.0  5.0 0   0.3                                                                               --    2.1  1521 1.8                                                                               10.sup.12                                *12                                                                               3.0  2.0 1.0 0  --    1.7  2115 1.7                                                                               10.sup.12                                13 3.0  3.0 3.0 0.3                                                                               --    2.2  2261 1.8                                                                               10.sup.12                                14 3.0  3.0 5.0 0.5                                                                               --    2.4  2319 1.6                                                                               10.sup.12                                *15                                                                               3.0  1.0 6.0 1.0                                                                               --    2.5  1638 1.9                                                                               10.sup.12                                *16                                                                               3.0  1.0 3.0 0  --    1.8  2126 1.8                                                                               10.sup.12                                17 3.0  1.0 3.0 0.1                                                                               --    2.4  2280 1.7                                                                               10.sup.12                                18 3.0  1.0 3.0 0.3                                                                               --    2.3  2236 1.7                                                                               10.sup.12                                19 3.0  1.0 3.0 0.5                                                                               --    2.3  2219 1.6                                                                               10.sup.12                                20 3.0  1.0 3.0 1.0                                                                               --    2.4  2034 1.7                                                                               10.sup.12                                *21                                                                               3.0  1.0 3.0 1.1                                                                               --    2.4  1570 1.7                                                                               10.sup.12                                22 3.0  1.0 3.0 0.5                                                                               MnO 0.3                                                                              2.3  2273 1.7                                                                               10.sup.12                                *23                                                                               3.0  1.0 3.0 0.5                                                                               MnO 0.6                                                                              2.2  2176 1.6                                                                               10.sup.12                                24 3.0  1.0 3.0 0.5                                                                               Cr.sub.2 O.sub.3                                                                   0.3                                                                              2.1  2369 1.6                                                                               10.sup.12                                *25                                                                               3.0  1.0 3.0 0.5                                                                               Cr.sub.2 O.sub. 3                                                                  0.6                                                                              2.5  2306 1.6                                                                               10.sup.12                                26 3.0  1.0 3.0 0.5                                                                               Fe.sub.2 O.sub.3                                                                   0.3                                                                              2.4  2219 1.6                                                                               10.sup.12                                *27                                                                               3.0  1.0 3.0 0.5                                                                               Fe.sub.2 O.sub.3                                                                   0.6                                                                              2.2  2189 1.5                                                                               10.sup.12                                28 3.0  1.0 3.0 0.5                                                                               NiO 0.3                                                                              2.3  2111 1.7                                                                               10.sup.12                                *29                                                                               3.0  1.0 3.0 0.5                                                                               NiO 0.6                                                                              2.2  2245 1.5                                                                               10.sup.12                                30 3.0  1.0 3.0 0.5                                                                               CoO 0.3                                                                              2.2  2275 1.7                                                                               10.sup.12                                *31                                                                               3.0  1.0 3.0 0.5                                                                               CoO 0.6                                                                              2.4  2284 1.6                                                                               10.sup.12                                __________________________________________________________________________      *Comparison example                                                            Remark: Among the additive composition MnO.sub.2 and the like of "other"       shows weight % to the main component.                                    

In the above-mentioned Table 8 through Table 10, the bending strength are lowered in comparison with the embodiments of Table 2 and Table 7. But, this is caused by narrowing of the span of the measuring jig from 2.5 mm to 2.0 mm; and in substance the bending force was improved, and effect of SiO₂ addition is observed. This SiO₂ addition does not make the effect of improving the bending strength under 0.1 weight parts, and lowers capacitance for addition exceeding 1.0 weight parts. Furthermore, it was confirmed that temperature characteristics are hardly influenced at the addition of 0.1-1.0 weight percent.

Nextly, laminated ceramic capacitors were trially made by using the ultrafine powder SiO₂ obtained by the vapor phase method of the sample 16 of the sixth embodiment. 200 pieces were sampled from each lot, and their bending strength were examined with 2.0 mm span shown in FIG. 8, and mean values of the bending strength and their coefficient of variation are shown in Table 13.

                  TABLE 13                                                         ______________________________________                                                               Bending  Coefficient of                                                        strength variation                                       SiO.sub.2 used                                                                            Lot No.    - x (Kg) σ/- x (%)                                 ______________________________________                                         Vapor phase                                                                               1          2.7      3.8                                             method                                                                         Ultra fine 2          2.8      2.9                                             powder SiO.sub.2                                                                          3          2.8      4.2                                             Precipitation                                                                             1          2.6      8.7                                             method                                                                         Fine powder                                                                               2          2.9      10.1                                            SiO.sub.2                                                                                 3          2.4      7.9                                             Conventional                                                                              1          2.8      13.4                                            example                                                                        Precipitation                                                                             2          2.3      16.7                                            method                                                                         granular SiO.sub.2                                                                        3          2.5      14.3                                            ______________________________________                                    

As is obvious from Table 13, the composition of the present invention has a high bending strength when using the ultrafine powder SiO₂ made by the vapor phase method, and the variations are decreased.

POSSIBLE UTILIZATION IN INDUSTRY

As has been explained above, according to the ceramic high dielectric composition of this invention, there are good characteristics when used as thin film type dielectric body such as laminated ceramic capacitor. That is, it has a composition to meet recent market needs in having high dielectric constant of 3000 or above, having small voltage-dependency, having strong bending strength and having small equivalent series resistance in high frequency, and has particularly high utility in the region of electronic tuner or the like. 

We claim:
 1. A ceramic high dielectric composition which consists essentially of, in parts by weight:1 to 5 parts CaTiO₃ 1 to 4 parts of Sb₂ O₃, and 1 to 5 parts of Nd₂ O₃ per 100 parts of BaTiO₃ as the host material, the ceramic composition having a dielectric constant ε25 of at least 3,000 measured at 25° C. with 1 KHz at 1 V(AC), tan δ not more than 2.0% measured at an effective voltage of 50 V/mm and a bending strength of at least 690 kg/cm².
 2. A ceramic high dielectric composition which consists essentially of, in parts by weight:1 to 5 parts of CaTiO₃, 1 to 4 parts of Sb₂ O₃, and 1 to 5 parts of La₂ O₃ per 100 parts of BaTiO₃ as the host material, the ceramic composition having a dielectric constant ε25 of at least 3,000 measured at 25° C. with 1 KHz at 1 V(AC), tan δ not more than 2.0% measured at an effective voltage of 50 V/mm and a bending strength of at least 690 kg/cm².
 3. A ceramic high dielectric composition which consists essentially of, in parts by weight:1 to 5 parts of CaTiO₃, 1 to 4 parts of Sb₂ O₃, and 1 to 5 parts of Sm₂ O₃ per 100 parts of BaTiO₃ as the host material, the ceramic composition having an dielectric constant ε25 of at least 3,000 measured at 25° C. with 1 KHz at 1 V(AC), tan δ not more than 2.0% measured at an effective voltage of 50 V/mm and a bending strength of at least 690 kg/cm².
 4. A ceramic high dielectric composition which consists essentially of, in parts by weight:1 to 5 parts of CaTiO₃, 1 to 4 parts of Sb₂ O₃, 1 to 5 parts of Nd₂ O₃, and 0.1 to 1 parts of SiO₂ per 100 parts of BaTiO₃ as the host material, the ceramic composition having a dielectric constant ε25 of at least 3,000 measured at 25° C. with 1 KHz at 1 V(AC), tan δ not more than 2.0% measured at an effective voltage of 50 V/mm and a bending strength of at least 690 kg/cm².
 5. A ceramic high dielectric composition which consists essentially of, in parts by weight:1 to 5 parts of CaTiO₃, 1 to 4 parts of Sb₂ O₃, 1 to 5 parts of La₂ O₃, and 0.1 to 1 parts of SiO₂ per 100 parts by weight of BaTiO₃ as the host material, the ceramic composition having a dielectric constant ε25 of at least 3,000 measured at 25° C. with 1 KHz at 1 V(AC), tan δ not more than 2.0% measured at an effective voltage of 50 V/mm and a bending strength of at least 690 kg/cm².
 6. A ceramic high dielectric composition which consists essentially of, in parts by weight:1 to 5 parts of CaTiO₃, 1 to 4 parts of Sb₂ O₃, 1 to 5 parts of Sm₂ O₃, and 0.1 to 1 parts of SiO₂ per 100 parts by weight of BaTiO₃ as the host material, the ceramic composition having a dielectric constant ε25 of at least 3,000 measured at 25° C. with 1 KHz at 1 V(AC), tan δ not more than 2.5% measured at an effective voltage of 50 V/mm and a bending strength of at least 690 kg/cm².
 7. A laminated ceramic capacitor made of the composition of claim
 1. 8. A laminated ceramic capacitor made of the composition of claim
 2. 9. A laminated ceramic capacitor made of the composition of claim
 3. 10. A laminated ceramic capacitor made of the composition of claim
 4. 11. A laminated ceramic capacitor made of the composition of claim
 5. 12. A laminated ceramic capacitor made of the composition of claim
 6. 